Process to preserve aqueous preparations of mineral materials, preserved aqueous preparations of mineral materials and use of preservative compounds in aqueous preparations of mineral materials

ABSTRACT

The present invention refers to a process for preserving an aqueous preparation of mineral material like e.g. calcium carbonate preparations, and to the use of a composition as a preservative in an aqueous preparation of mineral materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of U.S. application Ser. No. 13/637,991, filed Nov.6, 2012, which is a U.S. national phase of PCT Application No.PCT/EP2011/055023, filed Mar. 31, 2011, which claims priority toEuropean Application No. 10159511.4, filed Apr. 9, 2010 and U.S.Provisional Application No. 61/342,617, filed Apr. 16, 2010, thecontents of which are hereby incorporated by reference.

The present invention relates to a process for preserving an aqueouspreparation of mineral materials, to preserved aqueous preparationsobtained by this process and to the use of preservative compounds inaqueous preparations of mineral materials.

In practice, aqueous preparations of mineral materials are usedextensively in processes to prepare paper, paint, rubber and plastics,among other applications. For example, suspensions or dispersions ofcalcium carbonate, talc or kaolin are used in the paper industry in lameamounts as filler and/or as a component of paper coating formulations.Typical aqueous preparations of mineral materials are characterized inthat they comprise water, one or more mineral materials and optionallyfurther additives, such as dispersing and/or grinding aid agents,forming a suspension or dispersion with a solids content of 1 to 80% bydry weight relative to the total weight of the preparation. Polymers andcopolymers which may be used as dispersant and/or grinding aid agents insuch preparation are, for example, described in U.S. Pat. No. 5,278,248.

The aforementioned aqueous preparations are often subject tocontamination by microorganisms such as aerobic and anaerobic bacteriaresulting in changes in the preparation properties, such as changes inviscosity and/or pH, discolorations or reductions in other qualityparameters, which negatively affect their commercial value. Therefore,the manufacturers of such aqueous preparations usually take measures fordisinfecting and preserving the suspensions or dispersions. For example,EP 1 139 741 describes aqueous suspensions or dispersions of minerals,fillers and/or pigments, containing a microbiocidal agent in the form ofa solution and derivatives of phenol in partially neutralized form. WO01/85659 mentions aqueous formulations containing one or more phenolatesand at least one crystallization inhibitor that may be used to preservemineral slurries. U.S. Pat. No. 5,496,398 relates to a process for thereduction of microorganisms in kaolin clay slurries by a combination oflow temperature heat and reduced levels of a microbiocidal agent. WO02/052941 describes biocide compositions for incorporation into paints,coating, plasters and plastics comprising at least one metal oxide andat least one metal salt. U.S. Pat. No. 4,655,815 mentions aantimicrobial composition comprising a formaldehyde donor.

WO 2004/040979 A1 relates to synergic antimicrobial mixtures containing1,2-benzisothiazolinone (BIT) and benzylhemiformal (BHF). Thecorresponding mixtures are used, for example, for slurries of pigments.

For the purpose of the present invention, chemical means fordisinfection are referred to as “disinfectants” and are understood tocomprise substances that destroy microorganisms. For example, US2001/0009682 relates to disinfectant concentrates having improvedbiocidal activity which may contain an aldehyde such as glutaraldehyde,a glycol and a lithium based buffer. WO 2006/079911 mentions a processfor disinfection and/or preservation and/or reduction and/or control ofmicrobial contamination of aqueous dispersions and/or suspensions ofmineral matter, having at least one stage of increasing the OH⁻ ionconcentration of the aqueous dispersions or suspensions to a valuegreater than or equal to 1×10⁻² mole/l, and at least one stage ofdispersing and/or grinding the aqueous dispersions and/or suspensions.

For the purpose of the present invention, chemical means forpreservation are referred to as “preservatives” and are understood tocomprise substances inhibiting the growth and reproduction ofmicroorganisms. For example, US 2006/0111410 mentions a mixturecomprising 1,2-benzisothiazolinone (BIT) andtetramethylol-acetylenediurea (TMAD) for protecting industrial materialsand products against attack by microorganisms.

With regards to this latter class of preservatives used in aqueouspreparations of mineral materials, the classical example widely used inindustry is orthophenylphenol (OPP).

However, a recent European Council Directive has made it known that OPPwill be newly classified as a pesticide in food, feed and plantprotection applications. This new classification implies that many usersof aqueous mineral preparations requiring preservation will preferaqueous mineral preparations preserved with OPP alternatives that arenot associated with toxic residues on application, such as applicationsinvolving food contact, nor with toxic residues in waste products suchas waste water. Any manufacturing plant producing aqueous preparationsof mineral materials having one or more customers implementing suchpreparations in food, feed and plant protection application will then beobliged to globally implement an OPP alternative for essentially allcustomers due to the risk of OPP contamination throughout the plant.

Thus, there is a pressing need for adequate compositions providingsufficient preservation of aqueous preparations of mineral materialswithout implementing substances causing toxic residues.

In answer, the Application has surprisingly found a preservation systemmeeting these needs of the skilled man. Accordingly, first object of thepresent invention resides in a process for preserving an aqueouspreparation of mineral material, characterised in that the processcomprises the following steps:

(a) providing an aqueous preparation of at least one mineral material;

(b) adding to the aqueous preparation of step a) one or more sources oflithium ions in an amount such that the total amount of lithium ions inthe aqueous preparation is from 750 to less than 3 000 ppm, calculatedrelative to the water in the preparation;

(c) adding to the aqueous preparation of step a) one or more sources ofsodium and/or potassium and/or magnesium ions in an amount such that thetotal amount of sodium and/or potassium and/or magnesium ions in theaqueous preparation is from 3 000 to less than 7 500 ppm, calculatedrelative to the water in the preparation,

where steps (b) and (c) may be carried out simultaneously, or separatelyin any order.

According to the present invention, lithium, sodium, potassium andmagnesium ion contents in water can be evaluated by filtering off thesolids in the suspension by membrane filtration (pore size of 0.2microns) and measuring the content of these ions in the filtrate byliquid chromatography.

According to the present invention, preservation is evaluated as a lackof “significant growth” of bacteria over time starting from an aqueouspreparation of mineral material having a cfu/ml value (colony formingunit per milliliter) of less than 10⁴ cfu/ml. Said lithium and sodiumions are added to this starting aqueous preparation of mineral material.Thereafter, the aqueous preparation is inoculated with bacteria and thecfu/ml development is determined as described in the examples sectionhereafter. Significant growth means a growth of bacteria of greater thanthe error associated with the cfu/ml measurement technique.

The use of sodium bicarbonate alone as an inhibitor of bacterial growthin food has been described in Corral, L. et al, (“Research Note:Antimicrobial Activity”, Journal of Food Science, Volume 53, No. 3,1988, page 981), Table 1 of this publication shows that sodiumbicarbonate amounts required to inhibit growth are of the order of 1%.No mention is made of any use of lithium ions to allow far lower amountsof sodium bicarbonate to be employed in the context of an aqueouspreparation of mineral materials. Moreover, the bacterial speciestargeted are different from those typically found in the aqueouspreparations of the present invention.

Similarly, Wijnker J. et al. (“Antimicrobial properties of salt (NaCl )used for the preservation of natural casings”, Food Microbiology, Volume23, 2006, pages 657-662) disclose the use of sodium chloride as apreservative in food applications. Again, no mention is made of any useof lithium ions and the targeted bacterial differ from those typical ofan aqueous preparation of mineral material.

Finally, also in the context of food applications, sodium hydrogencarbonate is referred to in combination with ovotransferrin forproviding antimicrobial activity against L. monocytogenes and E. coli.

Relative to lithium ions, these are disclosed as enhancers ofaldehyde-releasing and/or aldehyde-based biocides in EP 2 108 260.

EP 1 623 725 discloses a kit to prepare a germicidal solution comprisingphlthalaldehyde and an enhancer for the phthalaldehyde, where saidenhancer may be a halide salt. EP 1 547 621 similarly mentions agermicidal dialdehyde enhanced by a halide salt.

EP 1 661 587 refers to a method of sealing a germicidal bicarbonatesolution in containers.

GB 1 443 786 claims a composition having biocidal and sporicidalactivity, which comprises a solvent which is water or a mixtures ofwater and a lower monohydric alcohol, glutaraldehyde and dissolvedquantities of at least one highly ionisable salt of a monovalent ordivalent cation base exchangeable with calcium, the composition having apH of 7 or less.

US 2006/0111410 refers to a mixture of biocidally active compounds,characterized in that it comprises tetramethyloacetylediurea (TMAD) and1,2-benzothiazoline (BIT) and/or its sodium, potassium or lithium salt.

U.S. Pat. No. 3,983,252 refers to a disinfectant composition comprisinga saturated dialdehyde containing from 2 to about 6 carbon atoms; analkali metal salt of a carboxylic acid containing from 2 to 25 carbonatoms and selected from the group consisting of sodium, potassium orlithium salts of alkanoic acids, sodium, potassium, or lithium salts ofalkenoic acids, and sodium, potassium or lithium salts of aromaticacids; and a member selected from the group consisting of lower alkanolscontaining up to and including 7 carbon atoms, alkanediols containingfrom 2 to 4 carbon atoms, glycerol and mixtures thereof, said alkalimetal salt of a carboxylic acid being present in a weight ratio to saiddialdehyde within the range of from about 0.05:1 to about 2:1, saidlower alkanol, alkanediol or glycerol being present in a weight ratio tosaid alkali metal salt of a carboxylic acid within the range of fromabout 1:0.1 to about 1:3, said composition when dissolved in waterproviding a solution having a pH of within the range of from about 6 toabout 7.4.

Finally, US 2001/0009682 refer to disinfectant concentrates havingimproved biocidal activity containing an aldehyde, such asglutaraldehyde, a glycol and a lithium based buffer.

Indeed, relative to the latter prior art documents, it is a remarkableadvantage of the present invention that no conventional biocide, such asan aldehyde-based biocide, is needed in order to obtain preservation ofan aqueous mineral preparation.

Aqueous Mineral Reparation of Step a)

According to step a) of the process of the present invention, an aqueouspreparation of at least one mineral material is provided.

Aqueous preparations in the meaning of the present invention comprisefilter cakes, suspensions or dispersions having a solids content of 1 to85%, preferably from 10 to 82%, and more preferably from 20 to 80%, bydry weight relative to the total weight of the aqueous preparation, asmeasured according to the measurement method provided in the examplessection hereafter.

Typically, the aqueous preparations of step a) have a pH value of 6 to10.5, and preferably of 7 to 10. The aqueous preparations of step a)preferably have a viscosity of from 50 to 800 mPa·s, and more preferablyof 80 to 600 mPa·s, as measured according to the measurement methodsgiven in the examples section herebelow.

The mineral material may be natural or synthetic and selected from thegroup consisting of calcium carbonate, such as ground calcium carbonateand precipitated calcium carbonate, kaolin, kaolinitic clay, calcinedkaolinitic clay, talc, calcium sulfate, quartz, attapulgite,montmorilionite, diatomaceous earth, finely divided silica, aluminiumoxide, aluminium hydroxide, silicates such as aluminium silicate,pumice, sepiolite, dolomite, composite pigment materials includingprecipitated calcium carbonate, mica, titanium dioxide, and mixturesthereof.

Preferably, said mineral material is a ground calcium carbonate, such aschalk, limestone, marble or mixtures thereof, a precipitated calciumcarbonate, dolomite, kaolin, kaolinitic clay, calcined kaolinitic clayor a mixture thereof.

Calcium carbonate (CaCO₃) e.g. is used as a coating and filling pigment,and is notably known to improve some of the optical properties of thefinal product, such as gloss, opacity or brightness. Calcium carbonatecan be of two types: ground or natural calcium carbonate referred to asGCC, and synthetic or precipitated calcium carbonate referred to as PCC.PCC may be rhombohedral and/or scalenohedral and/or aragonitic. The GCCor PCC may additionally be surface treated, for example with fatty acidssuch as stearic acid and corresponding calcium salts, and/or withsiloxane.

“Ground calcium carbonate” (GCC) in the meaning of the present inventionis a calcium carbonate obtained from natural sources, such as limestone,marble or chalk or dolomite, and processed through a treatment such asgrinding, screening and/or fractionizing by wet and/or dry, for exampleby a cyclone or classifier.

“Precipitated calcium carbonate” (PCC) in the meaning of the presentinvention is a synthesized material, generally obtained by precipitationfollowing reaction of carbon dioxide and lime in an aqueous environmentor by precipitation of a calcium and carbonate ion source in water.

Said GCC or PCC may, in one embodiment, be surface reacted to formasurface-reacted calcium carbonate, which are materials comprising GCCand/or PCC and an insoluble, at least partially crystalline,non-carbonate calcium salt extending from the surface of at least partof the calcium carbonate. Such surface-reacted products may, forexample, be prepared according to WO 00/39222, WO 2004/083316, WO2005/121257, WO 2009/074492, unpublished European patent applicationwith filing number 09162727.3, and unpublished European patentapplication with filing number 09162738.0.

Clay refers to crystalline small particles of mainly hydrous silicatesof aluminum, sometimes with magnesium and/or iron substitution for allor a part of the aluminium. The main groups of clay minerals are:kaolinite, the main constituent of kaolin; halloysite; illite;montmorillonite and vermiculite. The term “kaolinitic clay” used hereinrefers to a soft white clay that is composed mainly of the mineralkaolinite.

Kaolin is especially used in the paper industry, which uses them to coatand fill papers and boards and improves some of the optical propertiesof the final product, such as gloss, opacity or brightness. However,kaolin based products include paints, agricultural compositions, fibreglass products, polymer and rubber compositions, ceramic applications,catalyst supports, pharmaceuticals, cosmetics, adhesives, filter aids,and many more.

The mineral material of said preparation of step a) may have a particlesize distribution as conventionally employed for the material(s)involved in the type of product to be produced. For the purpose of thepresent invention, all particle size measurements are made in accordancewith the measurement methods given in the examples section hereafter.

In general, 90% of the particles will have an esd (equivalent sphericaldiameter) of less than 5 micron. Coarse minerals, filler or pigmentmaterials may have a particle esd generally (i.e., at least 90 wt.-%) inthe range of 1 to 5 microns. Fine minerals, filler or pigment materialsmay have a particle esd generally less than 2 microns, e.g. 50 to 99wt.-% less than 2 microns and preferably 60 to 90 wt.-% less than 2microns. It is preferred that the solid particles in the preparationhave a d₅₀ value of from 0.1 to 5 μm, preferably from 0.2 to 2 μm andmost preferably from 0.35 to 1 μm, for example 0.7 μm.

For keeping mineral particles suspended in an aqueous preparation andthus ensuring that the viscosity of the preparation remainssubstantially the same over time, additives such as dispersing agentsmay be used. A suitable dispersing agent according to the presentinvention is preferably made of monomers and/or co-monomers selectedfrom the group consisting of acrylic acid, methacrylic acid, itaconicacid, crotonic acid, fumaric acid, maleic anhydride acid, isocrotonicacid, aconitic acid (cis or trans), mesaconic acid, sinapinic acid,undecylenic acid, angelic acid, canellic acid, hydroxyacrylic acid,acrolein, acrylamide, acrylonitrile, dimethylaminoethyl methacrylate,vinylpyrrolidone, vinylcaprolactam, ethylene, propylene, isobutylene,diisobutylene, vinyl acetate, styrene, α-methyl styrene, methyl vinylketone, the esters of acrylic and methacrylic acids and mixturesthereof, wherein poly(acrylic acid) and/or poly (methacrylic acid) arepreferred as dispersing agent.

Lithium Ions of Step b)

According to step b) of the process of the present invention, one ormore sources of lithium ions are provided to the aqueous preparation ofstep a) in an amount such that the total amount of lithium ions in theaqueous preparation is from 750 to 3 000 ppm, calculated relative to thewater in the preparation.

Said lithium ions should be provided in a form such that on addition tosaid aqueous preparation of step a), the pH of said aqueous preparationremains in a range such that no dissolution of said mineral materialresults. For example, in the case of a calcium carbonate suspensionhaving a pH of between 7 and 10, the pH of this suspension should notdrop significantly below pH 7 on lithium ion addition, into a pH rangeimplying calcium carbonate dissolution.

Said lithium ions are preferably be provided in a form such that onaddition to said aqueous preparation of step a), the viscosity of saidaqueous preparation does not exceed 800 mPa·s.

Said lithium ions may be provided in the form of a water soluble lithiumcompound. Preferably, said water soluble lithium compound is selectedfrom lithium salts, and preferably from lithium carbonate, polymericsalts of lithium and mixtures of lithium carbonate with polymeric saltsof lithium. In a most preferred embodiment, said water soluble lithiumcompound is lithium carbonate.

In the embodiment where said water soluble lithium compound is a mixtureof lithium carbonate and polymeric salts of lithium, it is preferredthat the weight ratio of said lithium carbonate : polymeric salts oflithium is from 50:50 to 99.9:0.1.

Polymeric salt of lithium are preferably selected from lithium salts ofacrylic homopolymers, acrylic copolymers such as copolymers of acrylicacid and maleic acid and/or acrylamide, polyphosphates and mixturesthereof, said polymeric salt of lithium being more preferably aLi₂Na₂polyphosphate, lithium-sodium hexamethaphosphate or lithiumpolyacrylate. Li₂Na₂polyphosphate may be prepared by using an ionexchange technique (treatment of a cation exchanger in a column withlithium hydroxide and before passing a water based solution of Na₄P₂O₇from the top to the bottom of the column).

Said polymeric lithium salts are partially or completely neutralized,preferably to a degree of 5 to 100%, preferably to a degree of 25 to100% and most preferably to a degree of 75 to 100% using a neutralizingagent containing ions of lithium and, optionally other alkali metalsand/or alkaline earth metals. It is especially preferred that saidpolymeric salts of lithium are used wherein preferably at least 40mole-%, preferably 45 to 80 mole-% and more preferably 95 to 100 mole-%,of the acid sites of said polymeric salts of lithium are neutralized bylithium.

In an especially preferred embodiment the acidic sites of the polymericlithium salt are neutralized using a neutralizing agent containing onlylithium or lithium ions in combination with magnesium ions.

Neutralized polyacrylates and/or polymethacrylates with an averagemolecular weight of not more than 50,000, preferably with an averagemolecular weight in the range from 1,000 to 25,000 and more preferablyin the range from 3,000 to 12,000 are especially suitable.

It is to be noted that the aforementioned figures reflect the amount oflithium ions being added to the aqueous preparation, and do not coverany lithium ions which may naturally be present in the aqueouspreparation. However, the amount of naturally occurring lithium ions ine.g. a calcium carbonate slurry usually is negligible and well below 50ppm, based on the mineral material content of the aqueous preparation.

In a preferred embodiment, said lithium ions are provided to the aqueouspreparation of step a) in an amount such that the total amount oflithium ions in the aqueous preparation is from 750 to 1 500 ppm,calculated relative to the water in the preparation.

The optimum amount to be employed within the defined ranges can bedetermined by preliminary tests and test series on a laboratory scaleand by supplementary operational tests.

Sodium Ions of Step c)

According to step c) of the process of the present invention, one ormore sources of sodium and/or potassium and/or magnesium ions are addedto said aqueous preparation of step a) in an amount such that the totalamount of sodium and/or potassium and/or magnesium ions in the aqueouspreparation is from 3 000 to 7 500 ppm, calculated relative to the waterin the preparation.

Said sodium and/or potassium and/or magnesium ions should be provided ina form such that on addition to said aqueous preparation of step a), thepH of said aqueous preparation remains in a range such that nodissolution of said mineral material results. For example, in the caseof a calcium carbonate suspension having a pH of between 7 and 10, thepH of this suspension should not drop significantly below pH 7 onaddition of said sodium and/or potassium and/or magnesium ions, into apH range implying calcium carbonate dissolution.

Said sodium and/or potassium and/or magnesium ions are preferably beprovided in a form such that on addition to said aqueous preparation ofstep a), the viscosity of said aqueous preparation does not exceed 800mPa·s.

Said sodium and/or potassium and/or magnesium ions may be provided inthe form of a water soluble sodium and/or potassium and/or magnesiumcompound. Preferably, said water soluble sodium and/or potassium and/ormagnesium compound is selected from sodium and/or potassium and/ormagnesium carbonate, sodium and/or potassium and/or magnesium chloride,mixtures of sodium and/or potassium and/or magnesium chloride withpolymeric salts of sodium and/or potassium and/or magnesium, andmixtures of sodium and/or potassium and/or magnesium carbonate withpolymeric salts of sodium and/or potassium and/or magnesium. In a mostpreferred embodiment, said water soluble sodium and/or potassium and/ormagnesium compound is sodium and/or potassium and/or magnesiumcarbonate. In a most preferred embodiment, said sodium and/or potassiumand/or magnesium compound is sodium carbonate.

In the embodiment where said water soluble sodium and/or potassiumand/or magnesium compound is a mixture of sodium and/or potassium and/ormagnesium carbonate and polymeric salts of sodium and/or potassiumand/or magnesium, it is preferred that the weight ratio of said sodiumand/or potassium and/or magnesium carbonate : polymeric salts of sodiumand/or potassium and/or magnesium is from 80:20 to 99.9:0.1.

Polymeric salt of sodium and/or potassium and/or magnesium arepreferably selected from sodium and/or potassium and/or magnesium saltsof acrylic homopolymers, acrylic copolymers such as copolymers ofacrylic acid and maleic acid and/or acrylamide, polyphosphates andmixtures thereof, said polymeric salt of sodium being more preferably aLi₂Na₂polyphosphate, lithium-sodium hexamethaphosphate or lithiumpolyacrylate. Li₂Na₂polyphosphate may be prepared by using an ionexchange technique (treatment of a cation exchanger in a column withlithium hydroxide and before passing a water based solution of Na₄P₂O₇from the top to the bottom of the column)

Said polymeric sodium and/or potassium and/or magnesium salts arepartially or completely neutralized, preferably to a degree of 5 to100%, preferably to a degree of 25 to 100% and most preferably to adegree of 75 to 100% using a neutralizing agent containing ions ofsodium and/or potassium and/or magnesium and, optionally other alkalimetals and/or alkaline earth metals. It is especially preferred thatsaid polymeric salts of sodium and/or potassium and/or magnesium areused wherein preferably at least 40 mole-%, preferably 45 to 80 mole-%and more preferably 95 to 100 mole-%, of the acid sites of saidpolymeric salts of sodium and/or potassium and/or magnesium areneutralized by sodium and/or potassium and/or magnesium.

In an especially preferred embodiment the acidic sites of the polymericsodium and/or potassium and/or magnesium salts are neutralized using aneutralizing agent containing only sodium or sodium ions in combinationwith magnesium ions.

Neutralized polyacrylates and/or polymethacrylates with an averagemolecular weight of not more than 50,000, preferably with an averagemolecular weight in the range from 1,000 to 25,000 and more preferablyin the range from 3,000 to 12,000 are especially suitable.

It is to be noted that the aforementioned figures reflect the amount ofsodium and/or potassium and/or magnesium ions being added to the aqueouspreparation, and do not cover any sodium and/or potassium and/ormagnesium ions which may naturally be present in the aqueouspreparation. However, the amount of naturally occurring sodium and/orpotassium and/or magnesium ions in e.g. a calcium carbonate slurryusually is negligible and below 50 ppm, based on the mineral materialcontent of the aqueous preparation.

In a preferred embodiment, said sodium and/or potassium and/or magnesiumions are provided to the aqueous preparation of step a) in an amountsuch that the total amount of sodium ions in the aqueous preparation isfrom 5 000 to 7 000 ppm, calculated relative to the water in thepreparation.

The optimum amount to be employed within the defined ranges can bedetermined by preliminary tests and test series on a laboratory scaleand by supplementary operational tests.

Order of Steps

Said lithium ions of step b) and said sodium and/or potassium and/ormagnesium ions of step c) may be added to the aqueous preparation ofstep a) in any order. For example, they may be added together orseparately before and/or during storage or before and/or duringtransport of the aqueous preparations, in a manner known by the skilledperson.

In one embodiment, said lithium ions of step b) and said sodium and/orpotassium and/or magnesium ions of step c) are added simultaneously. Inthis embodiment, said lithium ions of step b) and said sodium and/orpotassium and/or magnesium ions of step c) may be pre-mixed prior toaddition to said aqueous preparation of step a).

In an alternative embodiment, said lithium ions of step b) and saidsodium and/or potassium and/or magnesium ions of step c) are addedseparately. In the case where said lithium ions are provided via apolymeric salt, it is preferred that the polymeric salt of lithium beadded prior to said sodium and/or potassium and/or magnesium ions. Inthe case where said sodium and/or potassium and/or magnesium ions areprovided in part via a polymeric salt, it is preferred that thepolymeric salt of sodium and/or potassium and/or magnesium be addedprior to said lithium ions.

It is preferred that said lithium ions and said sodium and/or potassiumand/or magnesium ions are added to said aqueous preparation of step a)under mixing.

Additional Process Steps

In addition to said lithium ions and said sodium and/or potassium and/ormagnesium ions, conventional biocides may additionally be added to saidaqueous preparation of mineral material. However, in a more preferredembodiment, no biocide in addition to the biocide formed on combininglithium with magnesium and/or sodium and/or potassium is employed in theprocess of the present invention.

In the less preferred embodiment where a conventional biocide isemployed, it is preferred that said biocide is a disinfectant, in whichcase it is most preferred that said disinfectant is added prior to saidlithium and sodium and/or magnesium and/or potassium ions. Saiddisinfectant may additionally be dosed following addition of saidlithium and sodium and/or magnesium and/or potassium ions.

Said biocide is preferably selected from aldehyde-based biocides,aldehyde-releasing biocides, isothiazoline biocide and mixtures thereof.

In accordance with the present invention, an “aldehyde-based biocide”refers to a biocide which has one or more aldehyde-group. Thealdehyde-based biocide of the present invention is preferably selectedfrom the group consisting of formaldehyde, acetaldehyde, glyoxal,succinaldehyde, glutaraldehyde, 2-propenal, phthalic dialdehyde andmixtures thereof, and preferably is formaldehyde, glutaraldehyde andmixtures thereof.

In accordance with the present invention, an “aldehyde-releasingbiocide” refers to a compound which is able to release mono- di-, and/ortri-aldehyde. Preferred aldehyde-releasing biocides according to thepresent invention include formaldehyde-releasing biocides,acetaldehyde-releasing biocides, succinaldehyde-releasing biocides,2-propenal-releasing biocides and mixtures thereof.

According to another embodiment, the aldehyde-releasing compound isselected from the group consisting of benzylalcoholmono(poly)-hemiformal, ethyleneglycolhemiformal(EGHF),[1,2-Ethanediylbis(oxy)]-bis-methanol,tetrahydro-1,3,4,6-tetrakis(hydroxylmethyl)imidazo[4,5-d]imidazole-2,5(1H,3H)-dione(also commonly referred to as TetraMethylolAcetyleneDiurea TMAD) andmixtures thereof.

In accordance with the present invention, an “isothiazoline biocide”refers to a biocide which comprises at least one isothiazoline group. Apreferred isothiazoline biocide is 2-methyl-4-isothiazoline-3-one (MIT),5-chloro-2-methyl-2H-isothiazolin-3-one (CIT),1,2-benzisothiazoline-3-one (BIT), or mixtures thereof.

According to another preferred embodiment of the present invention, thealdehyde-releasing and/or aldehyde-based biocide is used together withbiocides selected from the group consisting of5-chloro-2-methyl-2H-isothiazolin-3-one (CIT),2-methyl-2H-isothiazolin-3-one (MIT) and mixtures thereof.

In the case where biocide selected from aldehyde-based biocides,aldehyde-releasing biocides, isothiazoline biocide and mixtures thereofis employed, said biocide may advantageously be combined with amonoalcohol primary alkanol amine as described in unpublished Europeanpatent application filed under number 09178228.4.

Moreover, said process may comprise a step, subsequent to addition ofsaid sodium and/or potassium and/or magnesium ions and said lithiumions, of drying said aqueous preparation to obtain a dry product.

Obtained Preserved Preparation

Another object of the present invention resides in a preserved aqueouspreparation obtained by the process of the present invention.

According to the present invention, it is especially preferred that theaqueous preparation obtained by the process of the present invention ispreserved relative to bacteria selected from the group consisting ofThermus sp., Propionibacterium sp., Rhodococcus sp., Panninobacter sp.,Caulobacter sp., Brevundimonas sp., Asticcacaulis sp., Sphingomonas sp.,Rhizobium sp., Ensifer sp., Bradyrhizobium sp., Tepidimonas sp.,Tepidicella sp., Aquabacterium sp., Pelomonas sp., Alcaligenis sp.,Achromobacter sp., Ralstonia sp., Limnobacter sp., Massilia sp.,Hydrogenophaga sp., Acidovorax sp., Curvibacter sp., Delftia sp.,Rhodoferax sp., Alishewanella sp., Stenotrophomonas sp., Dokdonella sp.,Methylosinus sp., Hyphomicrobium sp., Methylosulfomonas sp.,Methylobacteria sp., Pseudomonas sp. and mixtures thereof, and morepreferably contains bacteria selected from the group consisting ofPseudomonas putida, Pseudomonas mendocina, Pseudomonas fluorescens,Pseudomonas alcaligenes, Pseudomonas pseudoalcaligenes, Pseudomonasentomophila, Pseudomonas syringae, Methylobacterium extorquens,Methylobacterium radiotolerants, Methylobacterium dichloromethanicum,Methylobacterium organophilu, Hyphomicrobium zavarzini and mixturesthereof.

Preferably, the preservation means that the treated aqueous preparationmaintains a cfu/ml value of less than 10⁴ cfu/ml, more preferably ofless than 10³ cfu/ml, and even more preferably of less than 10² cfu/mlon contamination with any of said bacteria.

Preferably, the inventive process and use provide preservation ofaqueous preparations for a time period of at least 2 days, morepreferably for at least 4 days, still more preferably for at least 6days and most preferably for at least 8 days.

Said preserved aqueous preparation obtained by the process of thepresent invention may find applications in paper making, such as inbased paper making and/or in paper coating formulations, and in paintformulations.

Said preserved aqueous preparation obtained by the process of thepresent invention may be dried to obtain a dry product. Such dryproducts notably find applications in plastic, food, feed and cosmeticapplications.

Use of a Preservative

The present invention also refers to the use of a composition comprising

(a) one or more sources of lithium ions in an amount such that the totalamount of lithium ions in the aqueous preparation is from 750 to lessthan 3 000 ppm, calculated relative to the water in the preparation, and

(b) adding to the aqueous preparation of step a) one or more sources ofsodium and/or potassium and/or magnesium ions in an amount such that thetotal amount of sodium ions in the aqueous preparation is from 3 000 toless than 7 500 ppm, calculated relative to the water in thepreparation;

as a preservative in an aqueous preparation of mineral materials.

In a preferred embodiment, no further additive providing biocidalactivity is employed.

The following examples may additionally illustrate the invention, butare not meant to restrict the invention to the exemplified embodiments.The examples below show the good microbiological preservation of theaqueous preparations of minerals materials according to the invention.

EXAMPLES

In all of the following examples, the particle size distributioncharacteristics are measured using a Sedigraph™ 5100 of MicromeriticsInstrument Corporation. The method and the instrument are known to theskilled person and are commonly used to determine grain size of fillersand pigments. The measurement is carried out in an aqueous solution of0.1 wt % Na₄P₂O₇. The samples are dispersed using a high speed stirrerand supersonics.

All BET specific surface area measurements, quoted in m²/g, are measuredaccording to ISO 4652.

All Brookfield-viscosities are measured with a Brookfield DV-IIViscometer equipped with a LV-3 spindle at a speed of 100 rpm and roomtemperature (20±3° C.).

All biocide and lithium, sodium, magnesium and potassium amounts quotedin ppm represent mg values per kilogram of water in the aqueouspreparation.

All quoted bacterial counts (values are in cfu/ml) in the Tablesherebelow are determined after 5 days following plate-out and inaccordance with counting method described in “Bestimmung von aerobenmesophilen Keimen”, Schweizerisches Lebensmittelbuch, chapter 56,section 7.01, edition of 1985, revised version of 1988.

Example 1 Preparation of Aqueous Mineral Preparations

a) Calcium Carbonate Slurry 1

Calcium carbonate slurry 1 was prepared by wet grinding, in are-circulating, horizontal 1.4 liter attritor ball mill (Dyno-Mill™), a76.4 wt.-% suspension of north-Norwegian marble having a starting esd(equivalent spherical diameter) of about 45 μm, in the presence of 0.6wt.-%, based on the total weight of dry calcium carbonate, of aradically polymerized polyacrylic acid (MW 6000 g/Mol, polydispersity2.6 determined by gel permeation chromatography), wherein 50 mole-% ofthe carboxylic acid groups are neutralized by sodium and the remaining50 mole-% of the carboxylic acid groups are neutralized by magnesium.Following grinding, the calcium carbonate in suspension had thefollowing particle size distribution:

Diameter (μm) wt.-% <2 91.5 <1 62.2 <0.2 17.9

The Brookfield-viscosity of the slurry was determined as 180 mPa·s.

The total soluble magnesium content was 21 ppm and the total solublesodium content was 927 ppm based on the weight of water in the slurry.

b) Calcium Carbonate Slurry 2

Calcium carbonate slurry 2 was prepared by wet grinding, in arecirculating, horizontal 1.4 liter attritor ball mill (Dyno-Mill™), a76.1 wt.-% suspension of north-Norwegian marble having a starting esd(equivalent spherical diameter) of about 45 μm, in the presence of 0.6wt.-%, based on the total weight of dry calcium carbonate, of aradically polymerized polyacrylic acid (MW 6000 g/Mol, polydispersity2.6 determined by gel permeation chromatography), wherein 100 mole-% ofthe carboxylic acid groups are neutralized by lithium. Followinggrinding, the calcium. carbonate in suspension had the followingparticle size distribution:

Diameter (μm) wt-% <2 90.5 <1 60.2   <0.2 15.0

The Brookfield-viscosity of the slurry was 130 mPa·s. The total solublelithium content was 800 ppm based on the weight of water in the slurry.

Example 2 Preservation Activity

The preservation activity of various embodiments of the presentinvention and of comparison examples was determined in the testsherebelow.

Tests a) Sodium and Lithium Ions

6 000 ppm of sodium ions, based on the weight of the water in thesuspension, provided in the form of a 1 M solution of sodium carbonate,were introduced into 50 g samples of calcium carbonate slurry 1. Inparallel, control samples of calcium carbonate slurry 1 were preparedwithout addition of further sodium ions.

The total sodium amounts listed in the Table below were calculated asthe amount of sodium ions added as sodium carbonate to calcium carbonateslurry 1, plus the amount of soluble sodium ions added via thepolyacrylic acid as mentioned above.

To the indicated samples, lithium ions were provided in the form oflithium carbonate, which was added in the form of a powder and mixedwith the suspension in the amounts indicated in the Table below.

Thereafter, half of the samples of calcium carbonate slurry 1 wereinoculated with either 1 mL of Pseudomonas species or 1 mL ofPseudomonas species that are resistant glutaraldehyde-isothiazolinemixtures (said mixtures being in the form of aqueous solutions of 21weight % glutaraldehyde, 0.25 weight % methylisothiazoline, and 0.75weight % chloromethylisothiazoline). Each of the samples was incubatedat 30° C. for 72 hours. Thereafter, a 1:10 dilution in phosphatebuffered saline (PBS) was plated on plate count agar (PCA). These plateswere incubated at 30° C. and analysed after 5 days.

Resistant Pseudomonas sp. Pseudomonas species Na (ppm No 1 350 ppm No750 ppm Slurry on water) lithium lithium lithium lithium Calcium 927 ppm>10⁴ >10⁴ >10⁴ >10⁴ carbonate slurry 1 Calcium 6 927 ppm >10⁴ <10² >10⁴<10² carbonate slurry 1

The results of the above table confirm that it is only when sodium isimplemented in combination with lithium in the appropriate amount thatthe bacterial count of the suspension falls to below 10⁴ cfu/ml.

Tests b) Potassium and Lithium Ions

6 000 ppm of potassium ions, based on the weight of the weight of waterin the suspension, provided in the form of a 1 M solution of potassiumcarbonate, was introduced into 50 g samples of calcium carbonateslurry 1. In parallel, control samples of calcium carbonate slurry 1were prepared in absence of any sodium. To the indicated samples,lithium ions were provided in the form of lithium carbonate, which wasadded in the form of a powder and mixed with the suspension in theamounts indicated in the Table below.

Thereafter, half of the samples of calcium carbonate slurry 1 wereinoculated with either 1 mL of Pseudomonas species or 1 mL ofPseudomonas species that are resistant glutaraldehyde-isothiazolinemixtures (said mixtures being in the form of aqueous solutions of 21weight % glutaraldehyde, 0.25 weight % methylisothiazoline, and 0.75weight % chloromethylisothiazoline). Each of the samples was incubatedat 30° C. for 72 hours. Thereafter, a 1:10 dilution in phosphatebuffered saline (PBS) was plated on plate count agar (PCA). These plateswere incubated at 30° C. and analysed after 5 days.

Resistant Pseudomonas sp. Pseudomonas species K (ppm No 1700 ppm No 1050ppm Slurry on water) lithium lithium lithium lithium Calcium 0 ppm >10⁴>10⁴ >10⁴ >10⁴ carbonate slurry 1 Calcium 6 000 ppm >10⁴ <10² >10⁴ <10²carbonate slurry 1

The results of the above table confirm that it is only when potassium isimplemented in combination with lithium in the appropriate amount thatthe bacterial count of the suspension falls to below 10⁴ cfu/ml.

Tests c) Sodium and Lithium Ions

2 250 ppm of sodium ions, based on the weight of the weight of water inthe suspension, provided in the form of a 1 M solution of sodiumcarbonate, was introduced into 50 g samples of calcium carbonate slurry1.

The total sodium amounts listed in the Table below were calculated asthe amount of sodium ions added as sodium carbonate to calcium carbonateslurry 1, plus the amount of soluble sodium ions added via thepolyacrylic acid as mentioned above.

To the indicated samples, lithium ions were provided in the form oflithium carbonate, which was added in the form of a powder and mixedwith the suspension in the amounts indicated in the Table below.

All of samples were then inoculated with 1 mL of Pseudomonas species.After inoculation, the samples were incubated at 30° C. for 72 hours.Thereafter, a 1:10 dilution in phosphate buffered saline (PBS) wasplated on plate count agar (PCA). These plates were incubated at 30° C.and analysed after 5 days.

Pseudomonas sp. Na (ppm No 2 250 ppm Slurry on water) lithium lithiumCalcium 3 177 ppm >10⁴ <10² carbonate slurry 1

The results of the above table confirm that it is only when sodium isimplemented in combination with lithium in the appropriate amount thatthe bacterial count of the suspension falls to below 10⁴ cfu/ml.

Tests d) Sodium or Potassium and Lithium Ions—Multiple Inoculations ofPseudomonas Species

The indicated amount of sodium or potassium ions, based on the weight ofthe weight of water in the suspension, as listed in the Tables below,provided in the form of a 1 M solutions of sodium or potassiumcarbonate, was introduced into 50 g samples of calcium carbonate slurry2. In parallel, control samples of calcium carbonate slurry 1 wereprepared in absence of any sodium or potassium.

All of samples were then inoculated three times with 1 mL of Pseudomonasspecies, After each inoculation, the samples were incubated at 30° C.for 72 hours. Thereafter, a 1:10 dilution in phosphate buffered saline(PBS) was plated on plate count agar (PCA). These plates were incubatedat 30° C. and analysed after 5 days.

Calcium Calcium Calcium Calcium carbonate carbonate carbonate carbonateslurry 2 slurry 2 slurry 2 slurry 2 Na (ppm on 0 3 000 4 500 6 000water) Li (ppm on 800 800 800 800 water) Inoculation 1 >10⁴ <10² <10²<10² Inoculation 2 >10⁴   10³ <10² <10² Inoculation 3 >10⁴ >10⁴ <10²<10²

Calcium Calcium Calcium carbonate carbonate carbonate slurry 2 slurry 2slurry 2 K (ppm on 0 4 500 6 000 water) Li (ppm on 800 800 800 water)Inoculation 1 >10⁴ <10² <10² Inoculation 2 >10⁴ <10³ <10² Inoculation 3>10⁴ >10⁴ <10²

The results of the above tables confirm that it is only when sodium orpotassium is implemented in combination with lithium in the appropriateamount that the bacterial count of the suspension falls to below 10⁴cfu/ml following at least one innoculation.

Tests e) Sodium or Potassium and Lithium Ions—Multiple Inoculations ofBiocide-Resistant Pseudomonas Species

The indicated amount of sodium or potassium ions, based on the weight ofthe weight of water in the suspension, as listed in the Tables below,provided in the form of a 1 M solutions of sodium or potassiumcarbonate, was introduced into 50 g samples of calcium carbonate slurry2. In parallel, control samples of calcium carbonate slurry 1 wereprepared in absence of any sodium or potassium.

All of samples were then inoculated three times with 1 mL of Pseudomonasspecies that are resistant glutaraldehyde-isothiazoline mixtures (saidmixtures being in the form of aqueous solutions of 21 weight %glutaraldehyde, 0.25 weight % methylisothiazoline, and 0.75 weight %chloromethylisothiazoline). After each inoculation, the samples wereincubated at 30° C. for 72 hours. Thereafter, a 1:10 dilution inphosphate buffered saline (PBS) was plated on plate count agar (PCA).These plates were incubated at 30° C. and analysed after 5 days.

Calcium Calcium Calcium Calcium carbonate carbonate carbonate carbonateslurry 2 slurry 2 slurry 2 slurry 2 Na (ppm on 0 3 000 4 500 6 000water) Li (ppm on 800 800 800 800 water) Inoculation 1 >10⁴ <10³ <10²<10² Inoculation 2 >10⁴ >10⁴ <10³ <10² Inoculation 3 >10⁴ >10⁴ >10⁴ <10²

Calcium Calcium Calcium Calcium carbonate carbonate carbonate carbonateslurry 2 slurry 2 slurry 2 slurry 2 K (ppm on 0 3 000 4 500 6 000 water)Li (ppm on 800 800 800 800 water) Inoculation 1 >10⁴ <10³ <10³ <10²Inoculation 2 >10⁴ >10⁴ >10⁴ >10⁴ Inoculation 3 >10⁴ >10⁴ >10⁴ >10⁴

The results of the above tables confirm that it is only when sodium orpotassium is implemented in combination with lithium in the appropriateamount that the bacterial count of the suspension falls to below 10⁴cfu/ml following at least one innoculation.

The invention claimed is:
 1. An aqueous preparation obtained by aprocess for preserving an aqueous preparation of mineral material,wherein the process comprises the steps of: (a) providing an aqueouspreparation of mineral material at a solids content of 10 to 85% by dryweight relative to the total weight of the aqueous preparation, whereinthe mineral material consists of ground calcium carbonate, precipitatedcalcium carbonate, dolomite, ground calcium carbonate surface treatedwith a fatty acid, precipitated calcium carbonate surface treated with afatty acid, surface reacted ground calcium carbonate, surface-reactedprecipitated calcium carbonate, or any mixture thereof; (b) adding tothe aqueous preparation of step (a) one or more sources of lithium ionsin an amount such that the total amount of lithium ions in the aqueouspreparation is from 750 to less than 3000 ppm, calculated relative tothe water in the preparation; and (c) adding to the aqueous preparationof step (a) one or more sources of sodium ions and/or potassium ions inan amount such that the total amount of sodium ions and/or potassiumions in the aqueous preparation is from 3000 to less than 7500 ppm,calculated relative to the water in the preparation, where steps (b) and(c) may be carried out simultaneously, or separately in any order, inorder to preserve the aqueous preparation of the mineral material sothat the aqueous preparation so preserved has a bacterial count of lessthan 10⁴ cfu/ml.
 2. The aqueous preparation according to claim 1, havinga solids content of 20 to 80% by dry weight relative to the total weightof the aqueous preparation.
 3. The aqueous preparation according toclaim 1, wherein the aqueous preparation of step a) has a pH value of 6to 10.5.
 4. The aqueous preparation according to claim 1, wherein theaqueous preparation of step a) has a pH value of 7 to
 10. 5. The aqueouspreparation according to claim 1, wherein the aqueous preparation ofstep a) has a viscosity of from 50 to 800 mPa·s.
 6. The aqueouspreparation according to claim 1, wherein the aqueous preparation ofstep a) has a viscosity of from 80 to 600 mPa·s.
 7. The aqueouspreparation according to claim 1, wherein the mineral material consistsof ground calcium carbonate obtained from marble, limestone and/orchalk.
 8. The aqueous preparation according to claim 1, wherein themineral material consists of precipitated calcium carbonate.
 9. Theaqueous preparation according to claim 1, wherein the source of thelithium ions is a water soluble lithium compound, a lithium salt,lithium carbonate, a polymeric salt of lithium, a mixture of lithiumcarbonate with a polymeric salt of lithium, or a lithium salt of anacrylic homopolymer, an acrylic copolymer, a copolymer of acrylic acidand maleic acid and/or acrylamide, a polyphosphate, or any mixturethereof.
 10. The aqueous preparation according to claim 1, wherein thesource of the lithium ions is a polymeric salt of lithium selected fromLi₂Na₂polyphosphate, lithium-sodium hexamethaphosphate, and lithiumpolyacrylate.
 11. The aqueous preparation according to claim 1, whereinthe source of the lithium ions is lithium carbonate.
 12. The aqueouspreparation according to claim 1, wherein the source of the lithium ionsis lithium carbonate and a polymeric salt of lithium at a weight ratioof lithium carbonate:polymeric salt of lithium from 50:50 to 99.9:0.1.13. The aqueous preparation according to claim 1, wherein the lithiumions are provided to the aqueous preparation of step a) in an amountsuch that the total amount of lithium ions in the aqueous preparation isfrom 750 to 1500 ppm, calculated relative to the water in thepreparation.
 14. The aqueous preparation according to claim 1, whereinthe source of the sodium ions and/or potassium ions is selected from thegroup consisting of a water soluble sodium compound, a water solublepotassium compound, sodium carbonate, potassium carbonate, sodiumchloride, potassium chloride, and any mixture thereof, a mixture of oneor more of sodium chloride and potassium chloride with a polymeric saltof one or more of sodium and potassium, and a mixture of one or more ofsodium carbonate and potassium carbonate with a polymeric salt of one ormore of sodium and potassium.
 15. The aqueous preparation according toclaim 1, wherein the source of the sodium ions and/or potassium ions isone or more of sodium carbonate and potassium carbonate.
 16. The aqueouspreparation according to claim 1, wherein the source of the sodium ionsand/or potassium ions is sodium carbonate.
 17. The aqueous preparationaccording to claim 1, wherein the source of sodium ions and/or potassiumions is provided to the aqueous preparation of step (a) in an amountsuch that the total amount of sodium ions in the aqueous preparation isfrom 5000 to 7000 ppm, calculated relative to the water in thepreparation.
 18. The aqueous preparation according to claim 1, whereinthe source of the lithium ions of step (b) and the source of the sodiumions and/or potassium ions of step (c) are added simultaneously to theaqueous preparation of step (a).
 19. The aqueous preparation accordingto claim 1, wherein the source of lithium ions of step (b) and source ofsodium ions and/or potassium ions of step (c) are added separately tothe aqueous preparation of step (a).
 20. The aqueous preparationaccording to claim 1, wherein when the source of lithium ions is apolymeric salt, the polymeric salt of lithium is added prior to thesource of sodium ions and/or potassium ions.
 21. The aqueous preparationaccording to claim 1, wherein when the source of sodium ions and/orpotassium ions is a polymeric salt, the polymeric salt of one or more ofsodium and potassium is added prior to the source of lithium ions. 22.The aqueous preparation according to claim 1, wherein no biocide otherthan the biocide formed by addition of lithium ions and sodium ionsand/or potassium ions is added.
 23. A preparation comprising a driedaqueous preparation, wherein the aqueous preparation is the aqueouspreparation according to claim
 1. 24. The aqueous preparation accordingto claim 1, which is preserved relative to bacteria selected from thegroup consisting of Thermus sp., Propionibacterium sp., Rhodococcus sp.,Panninobacter sp., Caulobacter sp., Brevundimonas sp., Asticcacaulissp., Sphingomonas sp., Rhizobium sp., Ensifer sp., Bradyrhizobium sp.,Tepidimonas sp., Tepidicella sp., Aquabacterium sp., Pelomonas sp.,Alcaligenis sp., Achromobacter sp., Ralstonia sp., Limnobacter sp.,Massilia sp., Hydrogenophaga sp., Acidovorax sp., Curvibacter sp.,Delftia sp., Rhodoferax sp., Alishewanella sp., Stenotrophomonas sp.,Dokdonella sp., Methylosinus sp., Hyphomicrobium sp., Methylosulfomonassp., Methylobacteria sp., Pseudomonas sp., and mixtures thereof.
 25. Theaqueous preparation according to claim 1, which is preserved relative tobacteria selected from the group consisting of Pseudomonas putida,Pseudomonas mendocina, Pseudomonas fluorescens, Pseudomonas alcaligenes,Pseudomonas pseudoalcaligenes, Pseudomonas entomophila, Pseudomonassyringae, Methylobacterium extorquens, Methylobacterium radiotolerants,Methylobacterium dichloromethanicum, Methylobacterium organophilu,Hyphomicrobium zavarzini, and mixtures thereof.
 26. An aqueouspreparation of mineral matter at a solids content of 10 to 85% by dryweight relative to the total weight of the aqueous preparation, and as apreservative: (a) one or more sources of lithium ions in an amount suchthat the total amount of lithium ions in the aqueous preparation is from750 to less than 3000 ppm, calculated relative to the water in thepreparation, and (b) one or more sources of sodium ions and/or potassiumions in an amount such that the total amount of sodium ions and/orpotassium ions in the aqueous preparation is from 3000 to less than 7500ppm, calculated relative to the water in the preparation, wherein themineral matter consists of ground calcium carbonate, dolomite, groundcalcium carbonate surface treated with a fatty acid, surface reactedground calcium carbonate, or any mixture thereof.
 27. The aqueouspreparation according to claim 26, wherein no biocide other than thebiocide formed by addition of lithium ions and sodium ions and/orpotassium ions is added.
 28. A base paper, paper coating or paintformulation prepared from or comprising the aqueous preparationaccording to claim 1 or a dried form thereof.
 29. A plastic, food, feedor cosmetic prepared from or comprising the aqueous preparationaccording to claim 1 or a dried form thereof.
 30. The aqueouspreparation according to claim 1, wherein the mineral material consistsof ground calcium carbonate surface treated with a fatty acid orprecipitated calcium carbonate surface treated with a fatty acid. 31.The aqueous preparation according to claim 1, wherein the mineralmaterial consists of surface reacted ground calcium carbonate or surfacereacted precipitated calcium carbonate.